Amide sulfonate surface active agents



agents which are also novel compounds of this invention 3,168,538 Patented Feb. 2, 1965 3,168,538 R1 Rg-o-oa-on-n AMIDE SULFONATE SURFACE ACTIVE AGENTS ll Hans S. Mannheimer, 23 Haines Cove Drive, R- H D ri iii i i s N 120 949 H CHTGECHFTTTOH This invention relates to novel compounds and also to 2- methods for producing them. In one of its more specific T aspects the invention is directed to novel compounds and H also to methods for making them.

Some of the novel compounds of this invention may Said salts, examples of which are said Salts I and II, as distinguished from internal salts, are external salts as shown in the illustrative structural formulas thereof. Moreover they are self-salts in that two or more moles of the same specie of compounds of Formula I may be are inexpensive and may be used as general purpose reacted with each other to produce such external salts detergents, textile treating agents, as emulsifying and 1 m specle y be reacted wlth 1 mole f a emulgating agents. They also find employment as comf F SP of mp n Formula I to p ponents in oosmefic preparations, d due to w i hi h internal self-salts :of difierent species coupled together for foaming and other characteristics find use as components eXample f- Salts and of course, more in a variety f Shampoo f l ti than twodifferent species, as for example, 3 or more may The novel amphoteric water soluble, surface active P Q 1f deslred themby to PmYide external selfsalts agents are of the following general Formula I and are m which the external Sam Such as Salt 11 may l external Salts d d by reacting h same or dif. be produced, with all three dlfferent species as reactants be employed as intermediates which may be converted 25 into novel highly water-soluble, vamphoteric, surface active agents finding application in IE1. number of different fields. Said water-soluble amphoteric, surface active ferent species of said compounds with each other: for the Pr 4 therebf- 40 I have discovered that said compounds of Formula I h a may be prepared by following a procedure hereinafter set forth. The reactants which are employed for the production of said novel compounds of Formula I may be produced from well known andreadily available starting materials. One ofsaidreactants is a novel sultone of mine hereinafter described and may be produced by the procedure hereinafter described, in which the com- R2 is an alkylene or hydroxy alkylene groups of 2 to 6 POnentS mp y d a Sodium bisulfite, pi y carbon atoms, or alkylene oxide adducts of said hydroxy and Sodium hydroxide, all being well kIlOWn and lk l groups, id dd t containing 1 15 lk l readily available compounds. Another of said reactants oxide groups Per hydroxy gmup thergin and R1 isselected is one or a combination of two or more compounds of from the group consisting of hydrogen, alkyl radicals of Formula II hereinafter described and capable of being 5 oapbon atoms and hydroxy valkyl nadigals f 2 produced by following the methods well known to the art. carbon atoms, and'alkylene oxide adducts of said hydroxy the Production of Said novel compounds of alkyl radicals, said adduots containing 1-15 moles of {111113 I p y my HOVel sultone described and aim d alkylene oxide per hydroxy group therein; M is hydrogen in y Patent PP 3611 120921 fi or it equivalent d efer bl an lk li metal i June 30, 1961, and since matured into US. Patent 3,100,- lent and for most purposes sodium or potassium; said 779 05-August 13, 1963; and 0f the following formula: alkylene oxides being of 2-4 carbon atoms; and x is 1-15.

wherein R is a hydrocarbon radical of 4 to 18 carbon atoms; each R is an alkylene group of 2-4 carbon atoms;

The novel salts are produced by reacting under certain 3: conditions of two or more moles of compounds of For- 5 mula I wherein M is attached to the 50;; group of 1 OH mole is replaced by another mole of such compound A thereby to become attached directly to the nitrogen of s said other mole which now has a hydrogen atom attached and a compound of fonc'wmg Formula II: margin 0 R1 R3-0(R30) PH While more than 3 moles of said compounds of For- R .JJJ .NI' R: N/ mula I may be reacted with each other under certain conditions, the following are illustrative examples of some H of said saltswhen only 2 and 3 moles respectively are as my reactants. reacted with each other and are known as Salts I and II" Said compounds of- Formula II may be produced by respectively: reacting one mole proportion of a monocarboxylic acid,

R--COOH, wherein R is a hydrocarbon radical of 4-18 carbon atoms, with one mole proportion of an appropriate diamine reactant. The resulting amide is then etherified by treating it with one or a combination of two ormore alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide in the manner well known to the art to provide alkylene oxide adducts whereby 1-15 moles thereof couple with available hydroxy groups therein. Examples of said diamine reactants are amino ethyl ethanol amine (NH C H NHC H OH), amino ethyl propanol amine (NH C H NHC H OH), amino ethyl butanol amino (NH C H NHC H OH), amino propyl ethanol amine (NH C H NHC H OH), ethyl amino ethyl ethanol amine etc.

The specific steps for carrying out said reaction between the appropriate diamine and the monobasic carboxylic acid for the production of compound of the following formula:

are well known to those skilled in the ant. Among the methods which may be employed for that purpose is those described in my US. Patent 2,781,378 issued on February 12, 1957. The production of the alkylene adducts therefrom by combining an alkylene oxide therewith for the production of compounds of Formula II may be effected in the manner well known to the art for the production of alkylene oxide adducts.

The organic acid reacted with a diamine, examples of which are hereinbefore set forth, is one of -19 carbon atoms and containing a single COOH group, or any of the available anhydrides of said acids and by the term monocarboxylic organic acid as used herein, Imean to include both the acid and theavailable anhydride thereof which I regard as the equivalent of the acid. These acids may be: the aliphatic open chain saturated or unsaturated fatty acids as well as said fatty acids containing substituents, such as aryl radicals, as for example, acids of the type of Twitchell fatty acids; cycloaliphatic carboxylic acids preferably containing no more than 4 condensed nuclei and examples of which are hexahydrobenzoic, resinic, and naphthenic acids; as well as aromatic and aromatic-aliphatic carboxylic acids, such as While carboxylic acids having any number of carbon atoms may be employed, I prefer to employ those having at least 5 carbon atoms and preferably 5-18 carbon atoms in straight chain relationship. The acids which I employ may be derived from a number of different sources. Among some of them are the acid components chosen from oil or fats of animal, marine or vegetable origin and these include; the acids of coconut, palm kernel, and palm oil, also of soybean, linseed, olive, rapeseed, cottonseed, peanut and castor oil which contain large proportions of unsaturated fatty acids and also the acids derived from tallow, fish and seal oils, whale or shark oils and the hydrogenated acids from these sources. Moreover, the synthetic high molecular weight fatty acids, obtained by the oxidation of paraffin wax and similar high molecular weight hydrocarbons by means of gaseous oxidizing agents may be employed. In addition the acid may be one of the resinic acids, such as abietic acid, or the napthenic acids and long chain fatty acids having an aromatic hydrocarbon radical connected directly with the aliphatic chain (Twitchell fatty acids) as are obtainable from oleic, ricinoleic, linoleic and similar unsaturated fatty acids. Instead of employing mixture of acids from oil, fats and resins, single acids may be used, for example caproic, pimelic, heptylic, caprylic, undecylic, lauric, palmitic, stearic, behenic, arachis, and carotic, oleic, erucic, linoleic linolenic. ricinoleic and myristic acids.

My novel sultone employed as a reactant herein may be prepared by employing the procedure set forth in the following Example A, all parts being given by weight unless otherwise specified.

Example A About 104 parts of sodium meta bisulfite Na S O were charged into a glass flask and then there was also charged into said flask 600 parts of water into which was dissolved 1 cc. of a 50% aqueous solution of NaOH thereby to dissolve said sodium meta bisulfite therein. The solution was then heated to about 90 C. and maintained at that temperature for a period of about 15 min- C. throughout said period. Thereafter and for the next 2 /2 hours, stirring of the mass was continued and its temperature maintained at 4750 C. Then with or without a reflux condenser coupled with said flask, the mass therein was heated to boiling and maintained in that condition for a period of about 1 hour. Then the mass in said flask is cooled to room temperature, is hereinafter known as Mass A, and consists essentially of an aqueous solution of the novel sultone, whose structural formula is hereinbefore set forth, and NaCl lay-product.

According to this invention said novel sultone may be reacted with one or a combination of two or more of said compounds of Formula II, in the mole proportion of about 1-2 moles of and preferably 1.2-1.8 moles of sultone to 1 mole of said compounds of Formula II. The aforesaid reaction is carried out under acidic conditions due to the fact that my novel sultone imparts a pH below 7 to said aqueous medium carrying it and the other reactant. Said reactant is preferably carried out in an aqueous medium and with the use of external heat to provide an aqueous solution of one or a combination of two or more compounds which are internal salts of the following Formula III:

When a small quantity, as for example 1 cc. of said aqueous solution of a compound of Formula III is added to cc. of clear tap water and shaken therewith, there is a change from clear to cloudy. This indicates its lack of water-solubility in low concentration in which said compounds normally would be used, as surface active, agents. I have discovered that the structure thereof may be changed thereby to convert and render them water-. soluble, in low concentrations as well as high concentra. tions, amphoteric and further characterizcdby having;

good surface activity, detergent and wetting properties and useful in shampoos, cosmetics, in the fields of treating of textiles, etc.

For the aforesaid purpose the novel compounds of Formula III may under alkaline conditions in an aqueous medium be heated thereby to convert them into said novel water-soluble amphoterics having the other foregoing properties and being compounds of said Formula I which are soluble in low and high concentrations in an aqueous medium whose pH may be as low as 1 and as high as 14.

The alkaline agent preferably employed to render said aqueous medium alkaline is an alkali metal hydroxide, such as NaOH, KOH or the like and the amount of said agent is preferably at least about 1 mole proportion thereof per mole proportion of said novel compounds of Formula III in said aqueous medium.

I have also discovered that said novel water-soluble amphoteric surface, active agents may be self reacted in the presence of an acidic agent, such as hydrochloric, acetic, hydroxyacetic, phosphoric acids, etc., to provide external self-reacted salts, such as Salts I and H respectively, for example, whose structural formulas are hereinbefore set forth; and are given herein by way of illustration and not limitation for the reason that more than 3 moles of compounds of Formula I may be reacted with each other to provide still high molecular weight similar salts.

The following are novel illustrative methods for producing novel illustrative compounds of this invention, all parts being given by weight, unless otherwise specified.

Example I Said entire Mass A which is an aqueous solution of about 130 parts (1 mole) of my novel sultone, in Example A herein is heated to 80 C. and while at that temperature there are added with stirring 336 (1 mole) of a compound, hereinafter referred to as compound X, of the following formula:

The aforesaid compound which is an internal salt is not water-soluble in low concentrations. This is evidenced when one cc. of said aqueous solution at the end of said 3 hour period is added to 100 cc. of clear tap water and shaken therewith it causes a change from clear to cloudy.

Then 88 parts of a 50% aqueous solution of NaOH is added slowly to said entire aqueous mass after said 3 hour periodwhile-constant stirring still is maintained'and' the entire mass is heated to and then maintained at a temperature of 75-85 C. for a period of about 3 hours thereby to provide an aqueous solution hereinafter knownas Solution 1 consisting essentially of water in which are dissolved the NaCl byproduct and novel amphoteric 1 of the following formula:

Said amphoteric 1 is water-soluble even in very low concentrations as evidenced by adding 1 cc. of said Solution 1 to cc. of water, which remain clear after said addition.

Examples 2 and 3 Employ the same procedure and components as set forth in Example 1, except that for the 330 parts (1' mole) of compound X employed therein, there are substituted 303 parts (1 mole) of a capri'c acid derivative and 415 parts (1 mole) of a stearic acid derivative respectively, which are the same as the compound X except that the radical (C H thereof is replaced by the respective (C H radical and the (C I-I radical whereby there are produced novel amphoterics 2 and 3 respectively, which are the same as amphoetric 1 except for the substitution of the C H and 0 1-1 radicals respectively for the C H radical of amphoteric 1.

Examples 4 and 5 Employ the same procedure and components as Exam-- ple 1 except that instead of the 330 parts of compound X of Example 1 there are employed 260 parts (.66 mole) and 355 parts (.66 mole) respectively of the following respective reactants:

to produce novel amphoterics 4 and 5 of the followingrespective formulas:

Examples 6-012 Employ the same procedure and components as those of Example 1 herein except thatfor the l moleproportion of compoundX, there may be substituted about .6-1 molevv proportion of any other compound which is the same as compound X, except that for the radical C H- thereof,

groups herein defined,

theothers as hereinbeforedefined-and/ or for the hydrogen on the amide nitrogen there is substituted any of the other R groups all specific examples of which are hereinbefore set forth so that there are produced literally hundreds of different amphoterics which are of the same formula as that of amphoteric l of said Example 1 herein except that for the radical C H thereof there is substituted any other hydrocarbon radical of 4-18 carbon atoms, and/ or for the specific C H OC H OH radical thereof, there is substituted any of the other aforesaid R O-(R -O)H radicals and/or for the hydrogen on the amide nitrogen there is substituted any of the other R groups.

All of said novel amphoterics of Examples l-S and 6on are water soluble surface active amphoterics having excellent water-solubility at high as well as very low concentrations and in aqueous solution having good foaming properties and find the uses hereinbefore set forth.

While fair yields of said novel compounds of Formula I may be obtained by employing respective quantities of my novel sultone and compound of Formula II in the mole proportion of 1 to 1 as in Examples 1-3 herein, it is preferable that the respective quantities of the sultone and the compound of Formula II be in the range of 1.2-1.8 moles of sultone per mole of compound of Formula H whereby high yields, measuring more than 90% of theoretical, of the novel amphoterics may be obtained. I have discovered also that when the respective quantities of sultone and compound of Formula II are in the mole proportion of approximately 1.5 of sultone to 1 of compound of Formula II, I obtain resultant aqueous solutions as end products which have unusual foaming properties when compared with corresponding end product produced in a system where the quantity of sultone and compound of Formula II is more or less than about 1.5 moles of sultone to 1 mole of compound of Formula II.

I have further discovered that said individual amphoteric compounds may be reacted with themselves or with each other to provide salts thereof. For this purpose there is added to the aqueous solution of the amphoteric prepared according to any of said examples a quantity of an acidic agent, such as HCl, to lower the pH thereof. In general, the quantity of HCl added is in the range of about /2 to 1 mole proportion of HCl per mole proportion of amphoteric of Formula I in solution. Then the aqueous mass is heated to 4050 C. and maintained at that temperature for about 10 minutes to provide the salts of the amphoteric employed, some general examples of such salts are said Salts I and II whose structural formulas are hereinbefore set forth and other of such salts in which more than three moles of the amphoteric employed have reacted to provide still longer chain salts then said Salt II. The length of the salt formation, examples of some of them being said Salts I and II, are dependent upon the concentration of the novel amphoterics of Formula I in solution, the temperature of the mass, the quantity of HCl employed, etc. In most instances the resultant salt formations are mixtures of salts of different lengths, all of which of course are salts of at least 2 moles of the amphoteric used.

The following are illustrative methods for producing such salts and are given by way of illustration and not limitation, all parts being given by weight unless otherwise specified.

Example 18 The entire Solution 1 of Example 1 herein is heated to 40 C. and while at that temperature there is added thereto about 100 parts of HCl (32% conc.) while stirring.

' The resultant mass is maintained at 40 C. while being constantly stirred for a period of about 5-10 minutes. By virtue of the foregoing the amphoteric 1 in said solution is converted into its externol salts of the type shown as Salts I and II herein and/or other salts of longer lengths but of the aforesaid type.

Said external self-salts, like compounds of Formula I,

are water-soluble, in low as well as high concentrations as evidenced by the fact that when 1 cc. of said solution containing said salts is added to cc. of clear tap water and shaken therewith, clearness is maintained. The aforesaid is not changed even when the pH of said solution is first adjusted to about 6.7 for comparative purposes.

If desired a mixture of two or more different amphoterics, such as a mixture of amphoterics 1, 2 and 3 for example may be treated in the same manner as above thereby to provide such salts of different amphoterics, with amphoterics 1 and 2, 2 and 3 and/or 1, 2 and 3, as well as 1 and 1, 2 and 2, and 3 and 3 being reacted with each other to provide salts of the type of Salts I and II heretofore shown structurally.

These external self-salts also have excellent watersolubility characteristics in high and low concentration, in aqueous solution are good foaming agents and have the same uses as the compounds of Formula I herein.

It is significant that in the production of aqueous solutions of compounds of Formula HI which have a pH of about 6.7 an example of which is such as solution thereof of Example 1 herein, that such solutions are not Watersoluble in low concentrations as hereinbefore set forth; whereas aqueous solutions of said external self-salts adjusted to a corresponding pH are water-soluble in correspondingly low concentrations. The foregoing clearly establishes that the internal salts of Formula III are different in character from the external self-salts hereinbefore described and that the treatment of compounds of Formula I result in the production of external self-salts and not a reversion to the internal salts.

As distinguished from the aforesaid my novel compounds of Formula I as well as the external self-salts thereof are soluble in clear water to provide clear solutions in all concentrations, that is high concentrations as well as low concentrations of 10% or less.

It is to be understood of course, that the respective definitions of R, R R R x, M are the same as they are used in the various formulas herein; and that wherever Na is used in any of the organic structural formulas in the description and claims herein, it is meant to cover its obvious equivalents, such as hydrogen, any other alkali metal or other equivalents well known to the art which may be substituted therefor; and that wherever caustic soda is employed in the description and claims, it is meant to cover its obvious equivalents, among which are KOH, as well as other appropriate alkalies.

It is to be understood that the following claims are intended to cover generic and specific features of the invention herein described and all statements of the scope of the invention which as a matter of language might be said to fall therebetween, and that they are intended to be inclusive in scope and not exclusive in that, if desired, other materials may be added to my novel produced herein claimed without departing from the spirit of the invention.

I claim:

1. A compound of the formula:

wherein R is a hydrocarbon radical of 4-18 carbon atoms; R is selected from the group consisting of hydrogen, alkyl radicals of 1-6 carbon atoms, hydroxy alkyl radicals of 26 carbon atoms and alkylene oxide adducts of said hydroxy alkyl radicals; R is selected from the class consisting of alkylene and hydroxy alkyene groups of 2-6 carbon atoms and alkylene oxide adducts of said hydroxy alkylene groups; said adducts containing 1-15 moles of alkylene oxide of 2-4 carbon atoms per hydroxy group; R is an alkylene group of 2-4 carbon atoms;

x is 1-15 and M is selected from the class consisting of hydrogen and alkali metals.

2. A salt of the formula:

wherein R is an aliphatic hydrocarbon radical of 4-18 1 carbon atoms; and x is 1-15. 3. A salt of the formula:

0 of 24 carbon atoms per hydroxy group, x is 1-15, y is is 0 or 1, and R is an alkylene group of 24 carbon atoms.

References Cited in the file of this patent Bergmann: The Chemistry of Acetylene and Related 15 Compounds, (1948), page 80.

Helberger et al.: Ann. Vol. 565, pages 22-35 (1949), Abstracted in Chemical Abstracts, vol. 44, col. 1892(a). (Abstract relied upon.) 

1. A COMPOUND OF THE FORMULA: 